2-alkyl spiro (4. 4) nonano (1, 2d) thiazole, quaternaries and process



Z-ALKYL SPIRO (4.4) NONANO (1,2d) THIAZOLE, QUATERNARIES AND PROCESS George de Stevens, New Providence, N.J., assignor to Sperry Rand Corporation, New York, N.Y., a corporation of Delaware No Drawing. Original application June 27, 1956, Serial No. 594,120. Divided and this application November 5, 1958, Serial No. 773,539

9 Claims. (Cl. 260-302) This invention relates to a new composition of matter. More particularly it relates to 2-alkyl spiro (4.4) nonano (1,2d) thiazole and a process for preparing same.

This application is a division of the co-pending application of George de Stevens, Serial Number 594,120, filed June 27, 1956, for Sensitizing Dyes Containing the Spiro (4.4) Nonano (1,2d) Thiazole Nucleus.

It has been found that the new thiazole compound of this invention has many useful properties. For example, it is possible to prepare cyanine dyes therefrom which are capable of sensitizing photographic emulsions strong-. ly and cleanly, i.e., without the production of excessive fog or residual dye stain.

It is known that cyanine dyes contain atleast two auxochromic nitrogen atoms, the one ternary and the' other quaternary, the one nitrogen atom lying in one heterocyclic nucleus and the other lying in another heterocy'clic nucleus, the two nitrogen atoms being connected by a conjugated carbon chain. With the thiazole compound of this invention, it is possible to prepare cyanine dyes in which one or both of the aforesaid auxochromic nitrogen atoms lie in a spiro (4.4) nonano (1,2d) thiazole nucleus.

Accordingly, it is the primary object of the present invention to provide the new thiazole compound 2-alkylspiro (4.4) nonano (1,2d) thiazole having the formula wherein R represents an alkyl radical C H and N is a positive integer of from one to three.

For a better understanding of the invention, together with other and further objects thereof, reference is had to the following description and its scope will be pointed out in the appended claims.

Generally speaking, the thiazole of this invention may be prepared by brominating spiro (4.4) nonan-l-one,

(Felinskii Comp. rend. acad. Sci. USSR 49, 568 (1945); 1

(IA. 40, 6058 (1946)) at position 2 to yield Z-bromo spiro (4.4) nonan-l-one, and then reacting the cool form of 2-bromo spiro (4.4) nonan-l-one with thioacetamide to yield 2-methyl spiro (4.4) nonano (1,2d) thiazole as follows: v

Br oal s -i; g (in 2 on, C-CH: CHQ/ on,

oar-43m EN i CH2 CH2 The following examples will serve to demonstrate the,

manner of preparation of the new thiazole of this invene 2,928,838 Patented Mar. 15, 1960 A solution of 27.0 g. (0.15 mole) of bromine in ml. of glacial acetic acid was added dropwise with stirring to a chilled (7 -10 C.) solution of 21.0 g. (0.15 mole) of spiro (4.4)-nonan-1-one in ml. of glacial acetic acid. Pentane (300 ml.) was added and the pentane solution was washed twice with water andtwice with sodium bicarbonate solution and dried over K CO;,'.- The-- volume of the pentane solution was reduced to 150 ml.

which, after chilling at -50 C., deposited a fine white precipitate. The product was collected at the pump,

' washed with chilled (-50 C.) pentane and driedoven CaCl The yield of 2-bromo ketone melting at 3 9'40 fwas 92% of theoretical. I

Example II.2-methylspiro (4.4) nonano (1,2d) thiaxole on: s v

0 a 04 E \o o'rn CHzCHz HPJIHI A mixture of 21.8 g. (0.1 mole) of 2-bromo (4.4) nonan-l-one and 7.5 g. (0.1 mole) of thioacetamide';

was heated slowly up to whereupon a vigorous reaction followed which was controlled by external cooling. c

The temperature of the reaction mixture did not rise.

above 127 and was maintained at 100 for l0'minutes.

The brown viscous mass was chilled and extracted with 20% aqueous hydrobrornic acid solution. The acid ex; tract, after thorough ether extraction, was made basic with NH OH and extracted with ether. The ether extract was then dried .over K CO After evaporation-of the, ether, the residue was distilled at reduced pressure giving,

. .rise to 22% yield of Z-methylspiro (4.4) nonano (1,2d)

thiazole, B.P. -95/0.5 mm.

' Example Ill.2-methylspir0 (4.4)nonano (1,211)

thiazole methiodide cm s 04 l C--C Hz A mixture of 0.5 g. (1 mo1.) of 2-rnethylspiro (4.4) nonano.(1,2d) thiazole, 1.0 g. (1 mol.+200% excess) ,of methyl iodide was refluxed for 24. hours. The chilled,

solution was triturated three times with 50 ml. portions of ether; The viscous residue was triturated with'3 of acetone and chilled for several hours, whereuponthe light yellow powder was collected .on a .filter, washed with-:- 2 ml. of cold acetone and air dried. The yield of crude product melting at 208210 was 40% of theoretical: Recrystallization from acetone (200 ml. per gram) gavef pure quaternary salt melting at 220-222 with decom position.

Found: 'N, 4.06%; S, 9.70%.

Analysis.-Calcd. for C12H18NSI: N, 4.18%, s, 3

masses Eiample lV; -2 methylspiro (4 .4 nomm-o (1,2'a7) thiazole .ethiodide.

fii CHr-GHz-- C5115, CliigCH2. A mixture of 4.0 g. (l moll) Z-methylspiro (4A.)

nonano (1,2d) thiazole and 7.0g. (1 mol.+200% excess) of ethyl iodide was=refluxedvfor 18 hours. The

V chilled solution was triturated-welliwith ether and then cold acetone giving ,rise. to :a light yellow powder: which was collected .omafilter, washed with. coldv acetone. and.

aim-dried; The yield of 1 crude quaternary: salt, .M.P. 178 2480?, was; 36% of: theoretical.

As: starting; material.v for the preparation oi. novel cyanine. dyes, tl1e 2-alkyl spiro (4.4-) non-ano (1,2d) .thiazole; particularly, 2-methyl. spit-o (4.4} nonano (1,2d) thiazole; is first converted to. a. quaternary salt. by re-.

actingit with an ester. such as settorth hereinabove -in.

Examples "3 and; 4s. Examples-.oflsuch esters arealkyl. halidesalkylsulfates, alkyl-p -toluene sulfonate,v ,etc.-. For purposesr of. convenience, the vquaternary; salts useful in preparing the'new cyauine dyes can: be represented. by.

the general formula r on, If o-a cur ous (JET- Hi wherein R represents an alkyl group, e.g., methyl, ethyl, n-propyl, isob'utyl, n-butyl,-. beta-hydroxyethyh. betamethoxyethyl," beta-eth'oxyethyl', beta-acetoxyethyh: beta carboxyethyl, carboxymethyl, beta-carbomethoxyethyl, beta=carbethoxyethyl, allyl, etc., or an aralkyl group;

esgr, benzyl; phenyl, etc., R represents methyl, ethyl or n-propyl and represents an anion, e.g., chloride bro-r mide, iodide," benzene sulfonate; p-toluenesulfonate, methyl" sulfate, ethylsulfate, thiocyanate, perchlorate,

eTd prepare :pseudocyanine dyes -fron1 su'ch quaternary salts; they are reacted with 2 halogenoquinoline:quater nary-salts the presence of an acid biuding -agent sucks 50 strong organic base such as triethylamine, trimethylaminep aaa'sodiunr-.-ethylatey sodium carbonata pyridine 0 ::;a

naphthothiazolei: salts, there" can" be preparedsitttpl cyaniue -dyesmtherfthanpgeudcicyaninedyes;

To "prepare; symmetrical carbocyanine dyes ffemrlfpresence-=of2 pyridine'oria mixture of pyridineand tri ethylaininer Tappepare-unsymmetrical .carbocyanine dyes from-"2 ulkylspiro 4.4) *nonano (13d? thiazole quaternary salts,

kylspir'o flii). nonanoi 1,2(1') thiazole quaternamr salts; the? quaternary -*'sal1s* are? reacted with esters, of. ortho aeidsfi SUClI'aS ethyl orthoformate,i; ethyl orthoacetate, ethyl orthopropionatwand ethyl orthobenzoate'" in-tlie a 4. they are reacted with cycloammoniui'n quateruarysalts containingabeta-aryl aminovinyl'group in. the alpha or gamma position, i.e., in one of the so-called reactive positions in the presence of an acid binding agent, e.g., pyridine or pyridine plus triethylarnine.

To prepare styryl dyesfrom-the new quaternary salts of this invention, they are condensed with pdialkyl aminobenza'ldehyderinthe presence'of an alkaline catalystsuch as piperidine 'in'absolute ethanol solution.-

T o prepare merocarboeyanine dyes from Z-alkyl spiro (4.4).nonano (1,2d). thiazole quaternary-salts, they-are condensed with ketomethylene heterocyclic intermediates containing an aryl aminomethylene group, in the 5-position inthepresence of'anacid binding agent, e.g., pyridineplus triethylamine. Examples-of such ketomethylene intermediates are 5-acetanilidomethylene-3-ethyl rhodanine, 5 acetanilidomethylene-Ii etliyl-1-phenyl 2 thiohydantoin, etc.

To sensitizephotographic.silver halide emulsions with the. aforesaid dyes, they. are dispersedin-the-emulsions such as the a conventional gelatino-silverhalide, I e."g.,. gelatino-silverbromide, bromoiodide, chloride and chlorobromide. emulsions are simple and well known to those skilled in the art, and described in various patents and publications.- Atypical method, for example, isithe' one described in U.S.-v Patent 2,336,843, patented December 14, 1943.-

Whileihere have been-describedwhat are at present considered'to be the preferred embodiments of this inven-- tion,.it=wil1 berobvious-to those skilled inthe-art that various changes and modificationsmay bezmade therein without. departing from the invention, and it is, th'erefore, intendedato-cover all such changes and modifications as fall .iwithinwth'e true". spirit and scope .of theinventione Whatisclaimed isz 1; The" new compound, Z-alkyl spiro' (4A) nonano (1,211) thiazole having the general formula:

CHaCH5 where R represents an alkyl radicalC I-I and n is a positive integer selected fromlthe group, one to three, both inclusive.

2. The new compound 2-methy1spiro (4.4) nonano (1,2d) thiazole having the structure?- CH2- H2 3; The. new compound consistingpf a quaternarysalt ofi'thercompounddescribed-fin claim" 1 having the"fo1-ilowing general .fdrmula:

where R represents an alkylradical C H gn is aipositive integer selected. from the grouprpne to ch-116e,. both inclusive, and Rfrepresents a member' selected from the group consisting of alltyl and aralkyl groups, and X rep- Themethods of incorporatingthesedyes in 5 6 4. The new compound Z-methyispiro (4.4) nonano 6. A process for preparing new Z-alkyl-spiro (4.4) (1,2d) thiazole methiodide having the structure: nonano (1,2d) thiazole bases consisting of reacting 2- 5 bromospiro (4.4) nonan-l-one with a thioamide selected from the group consisting of thioacetamide and thio- C i 5 propionamide.

7. A process for preparing Z-methyl-spiro (4.4) nonano c (1,2d) thiazoie consisting of reacting Z-bromospiro (4.4)

nonan-l-one with thioacetamide.

8. A process for preparing Z-methylspiro (4.4) nonano CH2-CH: 10 (1,2d) thiazole methiodide consisting of refluxing 2- 5. The new compound 2+methyispiro (4.4) nonano methylspiro (4.4) nonano (1,2d) thiazole with methyl (1,2d) thiazole ethiodide having the structure: iodide.

S 9. A process for preparing Z-methylspiro (4.4) nonano (1,2d) thiazole ethiodide comprising heating 2-methyl- 4 CF03, 15 spiro (4.4) nonano (1,2d) thiazole with ethyl iodide.

References Cited in the file of this patent g, UNITED STATES PATENTS 5 5 20 2,160,861 IIromatka June 6, 1939 

1. THE NEW COMPOUND, 2-ALKYL SPIRO (4.4) NONANO (1,2D) THIAZOLE HAVING THE GENERAL FORMULA:
 3. THE NEW COMPOUND CONSISTING OF A QUATERNARY SALT OF THE COMPOUND DESCRIBED IN CLAIM 1 HAVING FOL LOWING GENERAL FORMULA: 